O. Paleta et al. / Journal of Fluorine Chemistry 114 ꢀ2002) 51±53
53
with drying tube was charged with methacryloyl chloride
8.33 g, 79.7 mmol), triethylamine ꢀ8.06 g, 79.7 mmol),
Anal. Calcd. for C H F O : C, 28.4; H, 1.3. Found: C,
13 7 17 4
ꢀ
28.6; H, 1.5%.
diethyl ether ꢀ50 ml) and a stabilizer DPPH ꢀ10 mg) and
the mixture was stirred at r.t. for 1 h. A solution of ¯uor-
oalkanol 3 ꢀ35.8 g, 72.4 mmol) in diethyl ether ꢀ50 ml) was
then added dropwise and the mixture was stirred at r.t. for
Acknowledgements
1
NaHCO and the water layer was separated and extracted
2 h. The reaction mixture was neutralized with aqueous
The research has been supported by the Grant Agency of
the Czech Republic ꢀGrant no. 106/00/1296).
3
with diethyl ether ꢀ3 Â 30 ml). The organic solutions were
combined and dried over MgSO , which was ®ltered-off
4
after 10 h. Diethyl ether was removed from the ®ltrate by
rotary evaporator and the residue was trap-to-trap distilled in
vacuum to afford a mixture of unreacted 3 and product 4, bp
38±55 8C/1.2 mmHg. This raw material was repeatedly
fractionally distilled on a packed column ꢀsee compound
References
[
1] H.C. Fielding, in: R.E. Banks ꢀEd.), Organofluorine Chemicals and
Their Industrial Applications, Ellis Horwood, Chichester, 1979, p. 214.
[2] T.-M. Yong, W.P. Hems, J.L.M. van Nunen, A.B. Holmes, J.H.G.
Steinke, P.L. Taylor, J.A. Segal, D.A. Griffin, Chem. Commun.
3
1
): the ®rst distillation afforded pure 3 ꢀbp 61±63 8C/
3 mmHg), and a residue ꢀmixture of 3 and 4), which
was fractionally distilled to give two fractions, which each
ꢀ
1997) 1811.
[
[
[
[
3] M.J. Bowden, Materials for Microlithography, ACS Symposium
Series 266, Am. Chem. Soc., Washington, 1984, p. 10.
gave two fractions. The result was as follows: pure 3 ꢀ9.7 g,
4] B. Bednar, J. Devaty, J. Kralõcek, J. Zachoval, Org. Coat. Appl.
ÂÏ Â Â Â ÂÏ
27.2%); a mixture of 3 and 4 ꢀ6.22 g); almost pure 4, bp 91±
93 8C/22 mmHg, yield 1.82 g ꢀ4.5%), purity 96%; pure 4, bp
92±93 8C/22 mmHg, yield 10.13.2 g ꢀ24.9%). Stabilizer was
Polym. Sci. Proc. 48 ꢀ1983) 711.
5] G. Kuncov a , O. Paleta, J. G oÆ tz, V. D eÏ dek, J. Schr oÆ fl, J. Proch a zka,
Czech. Pat. 264 ꢀ1990) 639.
6] B.J. Tighe, Optical applications of fluoropolymers: contact lenses, in:
R.E. Banks ꢀEd.), Proceedings of the Fluoropolymers Conference
added to all distilled fractions.
1
992, UMIST, Manchester, 1992 ꢀChapter 11), and references therein.
4
.5.2. Procedure B
A mixture of methacryloyl chloride ꢀ15.7 g, 150 mmol),
[7] M.F. Refojo, in: M. Ruben, M. Guillon ꢀEds.), Contact Lens Practice,
Chapman & Hall, London, 1994 ꢀChapter 2).
[
8] B. Bedn a rÏ , V. Marou sÏ ek, J. Zachoval, O. Paleta, Czech. Pat. 273 782
1992); Chem. Abs. 120 ꢀ1993) 120754.
triethylamine ꢀ15.2 g, 150 mmol), ¯uoroalkanol 3 ꢀ24.7 g,
0 mmol), diethyl ether ꢀ100 ml) and stabilizer DPPH
10 mg) was prepared as in Procedure A and stirred at r.t.
ꢀ
5
ꢀ
Ï
[
9] O. Paleta, A. Danda, L. St eÏ p a n, J. Kv Âõ cÏ ala, V. D eÏ dek, J. Fluorine
Chem. 45 ꢀ1989) 331, and references therein.
for 4 h when a complete conversion of ¯uoroalkanol was
attained ꢀby 19F NMR). Methanol ꢀ1.6 g, 50 mmol) was then
[10] B. Am e duri, B. Boutevin, G. Kostov, Prog. Polym. Sci. 26 ꢀ2001)
105.
[
11] O. Paleta, V. C Âõ rkva, J. Kv Âõ cÏ ala, J. Fluorine Chem. 80 ꢀ1996) 125.
[
12] J. Kv Âõ cÏ ala, O. Paleta, V. D eÏ dek, J. Fluorine Chem. 47 ꢀ1990) 441.
[13] A.L. Logothetis, in: R.E. Banks, B.E. Smart, J.C. Tatlow ꢀEds.),
Organofluorine Chemistry: Principles and Commercial Applications,
Plenum Press, New York, 1994 ꢀChapter 16).
added and the mixture was stirred for an additional hour.
Water ꢀ2 Â 100 ml) was then added slowly to the mixture,
the ethereal layer was separated, the water layer was
extracted with diethyl ether ꢀ3 Â 50 ml); the ethereal solu-
[
[
[
14] E.L. Tatarinova, Ya.V. Zachinyaev, L.M. Popova, N.A. Ryabinin, A.I.
Ginak, Zh. Obshch. Khim. 62 ꢀ1992) 1677.
tions were combined and dried over MgSO . Diethyl ethyl
4
ether was evaporated by rotary evaporator, triethylamine,
methanol and methyl methacrylate were removed by dis-
tillation in vacuum ꢀ20±40 mmHg) and the residue was trap-
to-trap distilled as above. The raw product was fractionally
distilled as above to afford product 4 in a yield of 23.1 g
15] E.L. Tatarinova, Ya.V. Zachinyaev, L.M. Popova, N.A. Ryabinin, A.I.
Ginak, J. Gen. Chem. USSR 62 ꢀ1992) 1379.
16] M. Hudlicky, Chemistry of Organic Fluorine Compounds, 2nd
Revised Edition, Ellis Horwood/Prentice Hall, New York, 1992,
p. 182, and references cited.
Â
[
17] C.G. Krespan, Reduction, in: M. Hudlick y , A.E. Pavlath ꢀEds.),
Chemistry of Organic Fluorine Compounds II. A Critical Review,
Vol. 185, ACS Monograph 187, American Chemical Society,
Washington, DC, pp. 311±312, and references cited.
ꢀ
82%), bp 77±79 8C/13 mmHg.
1
H NMR ꢀ300.07 MHz, CDCl ): d 1.96 ꢀs, 3H, CH ), 4.68
3
3
3
ꢀ
3
d, 1H, CH2,
JHF 3:9 Hz), 5.7 ꢀs, 1H, CH =C), 6.19 ꢀs, 1H, CH =C).
JHF 5 Hz), 4.72 ꢀd, 1H, CH2,
[18] J. Svoboda, O. Paleta, V. D eÏ dek, Collect. Czech. Chem. Commun. 47
ꢀ1982) 3418.
2
2
1
9
F NMR ꢀ376.60 MHz, CDCl ): d À82.38 ꢀm, 2F,
3
[
19] V. C Âõ rkva, O. Paleta, J. Fluorine Chem. 94 ꢀ1999) 141.
[
20] V. C Âõ rkva, S. B oÈ hm, O. Paleta, J. Fluorine Chem. 102 ꢀ2000) 159.
[21] T. Martini, Ger. Pat. 2 461 445 ꢀ1976); Chem. Abstr. 85 ꢀ1976)
93865.
CF CF CF ), À80.85 ꢀm, 2F, OCFꢀCF )CF ), À80.57 ꢀm,
3
2
2
3
2
3
F, OCFꢀCF )CF ), À81.89 ꢀm, 3F, OCFꢀCF )CH O±),
3 2 2 3
3
2
3
2
À83.48 ꢀd, 3F, CF CF ), À130.21 ꢀs, 2F, CF CF ),
À134.44 ꢀm, 1F, CFCH O±), À145.69 ꢀm, 1F, OCFCF ).
[22] N. Ishikawa, M. Sasabe, J. Fluorine Chem. 25 ꢀ1984) 241.
2
3